Method for making carbon microfibers

ABSTRACT

A continuous fiber composite having carbon microfibers dispersed in the resin filling the interstices between the continuous fibers to enhance the transverse properties of the composite. The carbon microfibers are made by soaking carbon fibers in an intercalating acid solution comprising a mixture of fuming nitric and sulfuric acid to weaken the intercrystallite bonds. Gentle stirring of solution separates the carbon microfibers from the host fibers. The microfibers are then separated from the intercalating acid solution and washed to remove the residual acid.

This application is a division, of application Ser. No. 432,216, filedOct. 1, 1982, now U.S. Pat. No. 4,472,541.

BACKGROUND OF THE INVENTION FIELD OF THE INVENTION

The invention is related to the field of fibrous composite materials andin particular to a method for making carbon microfibers for secondarymatrix reinforcement of fibrous composites.

Prior Art

The use of fiber reinforced composite materials in the place of metalsand ceramics has been rapidly increasing. Carbon fiber reinforcedcomposites are currently receiving considerable attention because oftheir high strength to weight ratio, temperature resistance, corrosionresistance, impact strength, and other desirable properties. Workers inthe field have been continuously working to improve the strength of thecarbon fiber reinforced composites. The thrust of their efforts has beenalong two distinct paths. One has been to improve the strength andflexibility of the carbon fibers themselves as disclosed by Schulz inU.S. Pat. Nos. 4,138,525 and 4,014,725. The other has been directed tosurface treating the fibers to improve the adhesion between the fibersand the resins. Typical of this latter thrust are the methods disclosedby Lind et al in U.S. Pat. No. 4,269,876, Kalnin in U.S. Pat. No.4,073,869, Joo et al in U.S. Pat. No. 3,989,802 and others.

The physical properties of fiber reinforced composites along the fiberdirection are quite good and satisfactory for many applications. Incontrast however the physical properties of the fiber reinforcedcomposites transverse to the fiber direction is relatively low whencompared to those along the fiber direction. This is because thetransverse behavior is matrix dominated. This deficiency may bepartially rectified by fiber reinforcing the neat resin between theprimary reinforcing fibers with transverse discontinuous fibers. Thisrequires microfiber small enough to fit into the interstices between theprimary fibers. Commercially available microfibers, such as Wollastoniteor silicon carbide whiskers approach the desired size range.Wollastonite is a low cost mineral fiber with limited physicalproperties. In contrast silicon carbide whiskers have good physicalproperties but are very expensive. Therefore neither Wollastonite norsilicon carbide are well suited to interstitial reinforcement ofcontinuous fiber composites. The Wollastonite fibers are relativelylarge and the aspect ratio of the silicon carbide whiskers is notsufficiently uniform.

The present invention describes a method for making carbon microfibersthat have aspect ratios in the desired range and diameters sufficientlysmall to be used for the interstitial reinforcement of continuous fibercomposites.

SUMMARY OF THE INVENTION

The invention is a method for secondary reinforcement of continuousfiber composites using carbon microfibers and a method for making thecarbon microfibers. The carbon microfibers are made by immersingcommercially available carbon fibers in an intercalating acid solutioncomprising approximately 60% fuming nitric acid and 40% sulfuric acid ata temperature of approximately 85° C. for a period of time in excess of60 minutes to loosen the intercrystallite bonds between the graphiticplanes. The carbon microfibers are separated from the primary fibers bygently stirring the intercalating acid solution. The separatedmicrofibers are then filtered out of the solution and washed to removethe residual acid. The separated microfibers are then dispersed in theneat resin used to impregnate the interstices of the continuous fiber inthe fabrication of the continuous fiber composite. The composite is madeusing conventional methods with the carbon microfibers randomlydispersed between the interstices of the primary fibers.

One advantage of having the carbon microfibers dispersed in theinterstices of the continuous primary fibers is significant increase inthe transverse properties of the composite. Another advantage is thatthe microfibers may be made from scrap or chopped carbon fibers.

These and other advantages of the invention will become apparent from areading of the following detailed description of the invention and themethod for making the carbon microfibers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a microphotograph showing the onset of the fiber breakup afterbeing immersed in the intercalating acid solution for 30 minutes.

FIG. 2 is a microphotograph of the intercalating solution after 90minutes showing the separated microfibers.

FIG. 3 is a photograph taken with a scanning electron microscopeillustrating how the breakup of large carbon fiber gives rise to thevarious sizes and shapes of the microfibers produced by the disclosedmethod.

DETAILED DESCRIPTION OF THE INVENTION

Commercially available carbon fiber is typically about 8 microns indiameter. In this respect, carbon fibers are not unlike otherreinforcing fibers used in composite materials. However, unlike mostother reinforcing fibers, such as glass, carbon fiber possesses acomplex internal structure that contributes to its outstanding physicalproperties in the direction parallel to the fiber axis.

This structure has been elucidated by numerous workers in the field. Acomprehensive review of the carbon fiber structure is presented byReynolds in Chemistry and Physics of Carbon, Volume II, Dekker New York1973. Briefly, the carbon fiber structure consists of ribbon orfibrillar crystallites that twist, intertwine, and undulate along thelongitudinal axis of the fiber. The substructure of the ribbon orfibrillar crystallites is composed of aligned graphitic planes. Thesecrystallites may only be a few planes in thickness, but extend forhundreds of angstroms along the fiber axis.

High temperature heat treatment of the carbon fibers will improve thealignment of the fibers, reduce undulations of the ribbons, andsubstantially increase the longitudinal fiber modulus. The degree towhich these benefits are obtained depends to a large part upon the heattreatment as disclosed by W. Watts and W. Johnson in the Proceedings ofthe 3rd International Conference on Industrial Carbons and Graphite,London 1970, page 417.

The high degree of crystal alignment in ultra-high modulus fibersresults in relatively low tensile properties transverse to the fiberaxis due to weak Van der-Waals bonding between basal planes and reducedinterlocking. Therefore, it is reasonable to expect that such fiberswould split along the crystallite boundries into smaller particleshaving sufficiently high aspect ratios and small diameters to qualify asmicrofibers. Moreover, if the crystallites themselves were separatedfrom larger fibers, their physical properties would approach theoreticallimits.

In accordance with the above analysis, a method has been developed toproduce carbon microfibers small enough to fit into the intersticesbetween the primary fibers of a continuous fiber composite. The methodcomprises immersing the carbon fibers in a solution of two or morestrong intercalating acids to weaken and disrupt the intercrystallitebonding between the aligned graphitic planes. Mechanical agitation ofthe immersed fibers separates the crystallites whose inter-crystalliteboundries are weakened by the combination of intercalating acids fromthe immersed fibers. The residue of the carbon fibers is removed fromthe solution then the acid solution is diluted with water. The carbonmicrofibers are then separated from the diluted solution by filtering.Repeated washing and filtering steps are used to remove the residualacid from the separated microfibers.

A preferred solution of strong intercalating acid comprises a mixture of50 to 70 percent fuming nitric acid and 30 to 50 percent sulfuric acidand in particular a mixture containing 60 percent fuming nitric acid and40 percent sulfuric acid (95% aq.) at a temperature of 85° C.

As an example of the process, high modulus pitchbased carbon fiber, suchas Union Carbide P300 carbon fibers made by Union Carbide Corporation ofNew York, N.Y. was immersed in a mixture of 60% fuming nitric acid(HNO₃) and 40% sulfuric acid (H₂ SO⁴, 95% aq.) at 85° C. Gentle stirringaction was employed to agitate the fibers and separate the microfibersfrom the immersed fibers. After 30 minutes a sample of the fibers wasextracted and observed under a microscope. As illustrated in FIG. 1,which is a microphotograph of the withdrawn sample taken at 180×magnification, the onset of the fiber breakup is discernible. Inparticular one of the central fibers has become enlarged and splinteringmicrofibers are clearly visible. With further treatment in theintercalating solution the carbon microfibers separate from the basefibers and float free in the solution as illustrated in FIG. 2. FIG. 2is a microphotograph of the solution taken 90 minutes after the carbonfibers were immersed in the solution of intercalating acids and showsthe large quantity of high aspect ratio of carbon microfibers produced.A closer inspection of the splintering fibers using a scanning electronmicroscope is illustrated in FIG. 3. This photograph was taken at amagnification of 1.31K× and more clearly shows how the various sizes andshapes of microfiber are produced by this method. These microfibers maybe round, irregular or flat ribbons ranging from tenths of a micron toseveral microns in cross section.

As previously indicated the microfibers may be separated from thesolution by filtering. Repeated washings are used to remove the residualintercalating acid solution prior to incorporating them into continuousfiber composites.

One advantage of this method for making carbon microfibers is that theymay be produced at relatively low cost using scrap or chopped carbonfibers.

In the fabrication of the continuous fiber composite material theseparated carbon microfibers are dispersed in the resin material priorto impregnating the continuous fibers. The continous fiber composite ismade using the resin having the dispersed microfibers. As the primaryfibers are impregnated with the resin, the carbon microfibers becomerandomly dispersed in the interstices significantly enhancing thetransverse properties of the composite.

Although the invention has been described using carbon fibers and aparticular combination of intercalating acids, those skilled in the artwill recognize that the disclosed method is equally applicable to othermaterials and that other intercalating acids may be used to weaken theintercrystallite boundaries within the spirit of the invention asdescribed herein and set forth in the appended claims.

What is claimed is:
 1. A method for making carbon microfibers comprisingthe steps of:immersing carbon fibers in an intercalating acid solutionto weaken the intercrystal bonds betwen the crystallite planes of thecarbon fibers; stirring said intercalating acid solution with theimmersed carbon fibers to separate the weakened crystallite planes fromthe carbon fibers to form carbon microfibers; filtering saidintercalating acid solution to separate said carbon microfibers from theacid solution; and rinsing said separated carbon microfibers to removethe residual intercalating acid.
 2. The method of claim 1 wherein saidintercalating acid solution is a mixture of nitric acid and sulfuricacid.
 3. The method of claim 2 wherein said mixture comprises 50 to 70percent fuming nitric acid and the remainder sulfuric acid at atemperature between 80° C. and 90° C.
 4. The method of claim 2 whereinsaid mixture comprises 60 percent fuming nitric acid and 40 percentsulfuric acid at a temperature of 85° C.